US4238232A - Metallic modified material of intermetallic compound - Google Patents
Metallic modified material of intermetallic compound Download PDFInfo
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- US4238232A US4238232A US06/104,464 US10446479A US4238232A US 4238232 A US4238232 A US 4238232A US 10446479 A US10446479 A US 10446479A US 4238232 A US4238232 A US 4238232A
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- 239000000463 material Substances 0.000 title claims abstract description 69
- 229910000765 intermetallic Inorganic materials 0.000 title claims abstract description 29
- 239000004065 semiconductor Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 9
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 claims description 52
- 230000008859 change Effects 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 description 30
- 238000004544 sputter deposition Methods 0.000 description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 16
- 239000013078 crystal Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 238000000151 deposition Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 6
- 229910007709 ZnTe Inorganic materials 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052984 zinc sulfide Inorganic materials 0.000 description 6
- 229910004613 CdTe Inorganic materials 0.000 description 5
- 229910000673 Indium arsenide Inorganic materials 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 229910005542 GaSb Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 4
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 229910017115 AlSb Inorganic materials 0.000 description 3
- 229910002665 PbTe Inorganic materials 0.000 description 3
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 229910021480 group 4 element Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 229910021478 group 5 element Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002186 photoelectron spectrum Methods 0.000 description 2
- 239000002887 superconductor Substances 0.000 description 2
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910005642 SnTe Inorganic materials 0.000 description 1
- -1 ZnS Chemical class 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910000070 arsenic hydride Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910021476 group 6 element Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0623—Sulfides, selenides or tellurides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/02546—Arsenides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/02549—Antimonides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/20—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIIBV compounds
- H01L29/201—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIIBV compounds including two or more compounds, e.g. alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/26—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, elements provided for in two or more of the groups H01L29/16, H01L29/18, H01L29/20, H01L29/22, H01L29/24, e.g. alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S420/00—Alloys or metallic compositions
- Y10S420/903—Semiconductive
Definitions
- the present invention relates to a new metallic modified material having the same chemical composition as an intermetallic compound semiconductor but differing in crystalline structure and a process for the production of the same.
- Group III-V compounds having a zincblende-type or wurtzite-type crystalline structure such as InSb, InAs, InP, GaSb, GaAs, GaP, etc.
- Group II-VI compounds such as ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, BeO, etc.
- Group I-VII compounds such as CuCl and Group IV-VI compounds having a rocksalt type crystalline structure such as PbS, PbSe, PbTe, SnTe, etc.
- amorphous semiconductors of intermetallic compounds are formed on substrates by vacuum deposition method or by sputtering method.
- intermetallic compound semiconductors When intermetallic compound semiconductors are exposed to a high pressure at room temperature, for example, InSb, GaSb, AlSb, etc. are transformed into a white-tin-type crystalline structure and InAs, InP, ZnSe, ZnTe, CuCl, etc. are transformed into a rocksalt type crystalline structure, thus behaving themselves like a metal.
- phase transition into the semiconductor phase takes place when the pressure is lowered to normal pressure.
- the high pressure metallic phase of Group III-V compounds is obtained as a metastable phase when the pressure is lowered to normal pressure at 77° K.
- an amorphous InSb semiconductor is transformed into a material of rocksalt-type crystalline structure under a high pressure such as of about 10 Kbar, which is further transformed into a material of white-tin-type crystalline structure under a high pressure such as about 30 Kbar and which is transformed into a mixture of zincblende-type crystalline structure and rocksalt-type crystalline structure when the pressure is lowered to normal pressure.
- a high pressure such as of about 10 Kbar
- a metallic modified material of intermetallic compound which has the same chemical composition as an intermetallic compound semiconductor with a zincblende-type or wurtzite-type crystalline structure and further has a rocksalt-type crystalline structure and which is stable at room temperature to a predetermined temperature under normal pressure to high pressure, and by a process for the production of a metallic modified material of intermetallic compound which comprises depositing from a target consisting of an intermetallic compound semiconductor with a zincblende-type or wurtzite-type crystalline structure a metallic modified material of intermetallic compound with a rocksalt crystalline structure and the same chemical composition as the target on a substrate by tetrode-type sputtering.
- FIG. 1 is a schematic view of tetrode-type sputtering system used in the present invention
- FIG. 2 is a graph showing the relation of the threshold value of anode voltage and the current
- FIG. 3 is X-ray diffraction patterns of rocksalt-type InSb and zincblende-type InSb for comparison,
- FIG. 4 is a graph showing the results of differential thermal analysis as to the metallic modified material of InSb having a rocksalt crystalline structure according to the present invention
- FIG. 5 are photoelectron spectra of valence bands of the metallic modified material (a) consisting of rocksalt-type InSb and zincblende-type single crystal semiconductor (b),
- FIG. 6 is a graph showing the thermal effect of from room temperature to 4.2° K. on the resistivity of the metallic modified material of InSb,
- FIG. 7 is a graph showing the change of volume and lattice constant with pressure
- FIG. 8 is a cross sectional view of a heterojunction device consisting of a thin film and substrate and
- FIG. 9 is a cross sectional view of a semiconductor-superconductor heterojunction device consisting of a multilayer of thin films and substrates.
- a metallic modified material (metallic modifications) of intermetallic compound which has the same composition as an intermetallic compound semiconductor with a zincblende type or wurtzite type crystalline structure and further has a rocksalt-type crystalline structure and which is stable at room temperature to a predetermined temperature under atmospheric pressure to high pressures.
- the intermetallic compound is selected from the group consisting of Group III-V compounds, Group II-VI compounds, Group I-VII compounds, Group IV-VI compound-containing mixtures with these compounds and mixtures thereof.
- the deposition can be carried out in the presence of at least one reactive gaseous composition comprising at least one component selected from Group II, III, IV, V and VI elements.
- a target of a zincblende-type semiconductor consisting of two components selected from Group III elements and Group V elements is deposited the metallic modified material of intermetallic compound having the same chemical composition as the target and a rocksalt-type crystalline structure on a substrate by tetrode sputtering.
- a metallic modified material of intermetallic compound consisting of at least three components, the content of the each component being 1% or more, and having a rocksalt-type crystalline structure on a substrate by tetrode sputtering.
- a target consisting of a combination of two kinds of semiconductors of Group III-V compounds with other Group III-V compounds, Group IV elements or Group II-VI compounds and at least one reactive gaseous composition comprising at least one component selected from the above described elements is deposited a metallic modified material of intermetallic compound consisting of at least the three components, the content of the each component being 1% or more, and having a rocksalt-type crystalline structure on a substrate by discharge using a tetrode sputtering apparatus.
- These metallic modified material of intermetallic compounds can be deposited on a glass substrate, single crystal substrate or polycrystalline substrate as a bulky sample by controlling the anode voltage of a tetrode sputtering apparatus to a threshold value or more. According to the present invention, it is further found that the crystalline structure of such a metallic modified material is controlled by the anode voltage of tetrode sputtering but is independent on the variety or state of a substrate and on the deposition rate on a substrate.
- FIG. 1 shows a schematic view of tetrode sputtering apparatus suitable for the purpose of depositing a metallic modified material of intermetallic compound having a rocksalt-type crystalline structure.
- four electrodes i.e., cathode 1, anode 2, target 3 and auxiliary anode (stabilizer) 4 are arranged and substrate 5 is fitted to the surface of substrate holder 6 in parallel to target 3 to be apart therefrom by about 20 cm, the target having shield plate 7.
- Vacuum chamber 8 is evacuated from exhaust port 9 to 1 ⁇ 10 -8 Torr and high purity argon gas is fed from inlet 10 while keeping the evacuation to keep the pressure at about 2-8 ⁇ 10 -4 Torr.
- Direct current is passed through cathode 1 to emit thermoelectrons and a constant voltage of 300 V is applied to auxiliary anode 4 to bring the thermoelectrons into collision with the argon atoms and to induce ionization of the argon atoms, thus generating a plasma P.
- the voltage of the argon plasma is controlled by applying a certain voltage to anode 2.
- 11 is an inlet for a reactive gas
- 12 is a radio frequency power supply
- 13, 14 and 15 are respectively direct current power supplies.
- the metallic modified material of intermetallic compound according to the present invention is deposited on the substrate by applying generally to anode 2 a voltage of more than the threshold value of about 60 V, preferably, 90 to 150 V to control the voltage of argon plasma P, while a crystal of intermetallic compound or amorphous semiconductor is deposited on the substrate by applying generally a voltage of less than the threshold value of about 60 V to anode 2.
- the crystalline structure of such a deposited material depends on the voltage applied to anode 2. However, control of the pressure of pure argon gas introduced into vacuum chamber 8 (2-8 ⁇ 10 -4 Torr) and the high frequency voltage applied to target 3 ( ⁇ 1-2 kV) does not affect the crystalline structure of a deposited material, but affects the deposition rate.
- a metallic modified material with a rocksalt-type crystalline structure is deposited from a semiconductor target of indium antimonide (InSb) with a zincblende-type crystalline structure.
- InSb indium antimonide
- a semiconductor target of indium antimonide is fitted to a tetrode sputtering apparatus and a sample is prepared on a glass substrate or crystal substrate at a deposition rate of about 1 ⁇ m/hr by evacuating previously the vacuum chamber to a vacuum degree of 1 ⁇ 10 -8 Torr, introducing high purity argon gas with keeping the pressure at 2-8 ⁇ 10 -4 Torr, applying a voltage to the anode with varying from 20 V to 150 V and applying a high frequency voltage of ⁇ 1-2 kV to the target.
- FIG. 2 is a graph showing the relation of the threshold value of anode voltage with the current, in which the right side of the threshold value shows the rocksalt-type zone and the left side shows the amorphous zone.
- FIG. 3 shows X-ray diffraction patterns of the metallic modified material of indium antimonide having a rocksalt-type crystalline structure, deposited on a glass substrate by the above described method (upper graph) and the known polycrystalline semiconductor of indium antimonide having a zincblende-type crystalline structure (lower graph). The each peak is marked with the plane index.
- the plane (1 0 0) of the rocksalt-type polycrystal is oriented in parallel to the surface of the substrate and when the substrate is heated at 200° C., for example, the rocksalt-single crystal is obtained.
- X-ray diffraction test of the rocksalt-type modified material of indium antimonide teaches that it has a lattice constant of 6.11 A and a density of 6.92 g/cm 3 .
- FIG. 4 is a graph showing the results of differential thermal analysis of the metallic modified material of indium antimonide having a rocksalt-type crystalline structure according to the present invention.
- This new material is exothermically transformed into a material having a zincblende-type crystalline structure at 215° C. by heating under normal pressure at a heating rate of 10° C./min but remains metastable even by heating at 200° C. for a long time.
- FIG. 5 shows the difference of the photoelectron spectra of valence bands as to (a) the rocksalt-type metallic modified material of indium antimonide and (b) the zincblende-type single crystal semiconductor.
- FIG. 6 shows the temperature effect of from room temperature to 4.2° K. on the resistivity of the metallic modified material of indium antimonide.
- the electrical resistivity ⁇ of this new material being substantially independent upon temperatures, is about 3 ⁇ 10 -4 / ⁇ .cm.
- the Hall coefficient R H is about 3 ⁇ 10 -3 cm 3 /C and the polarity of the Hall voltage is negative. Assuming that electric current consists of electrons only, an electron density of electric current of about 2.1 ⁇ 10 21 cm -3 is determined from the value of the Hall coefficient.
- This new material shows a superconductive transition at 3.4 ⁇ 0.2° K. and a very high crystical magnetic field such as 9 to 10 KG. This new material can be used as a high accuracy resistor utilizing the phenomenon that the electric resistivity is independent upon temperatures.
- the rocksalt-type modified material of indium antimonide deposited by tetrode sputtering shows no phase transition under a pressure of up to about 80 Kbar at room temperature.
- FIG. 7 shows the change of the volume and lattice constant of this new material with pressures (V/Vo and a/a o respectively).
- a compressibility of 2.5 ⁇ 10 -6 bar -1 and a bulk modulus of 400 Kbar are determined from the pressure-volume curve in the 0-20 Kbar zone.
- the rocksalt-type modified material transformed from an amorphous semiconductor by pressure is transformed into a material of white-tin-type crystalline structure under a pressure of about 30 Kbar, which is transformed into a mixture of a zincblende-type modified material and rocksalt-type modified material if the pressure is lowered to normal pressure, which is thus different from the rocksalt-type modified material deposited by tetrode sputtering.
- a metallic modified material having a rocksalt-type crystalline structure of intermetallic compound consisting of at least three components is deposited from a target consisting of a combination of at least two kinds of semiconductors selected from Group II, Group III, Group IV, Group V and Group VI elements.
- a target consisting of a combination of two kinds of semiconductors as described above is fitted to a tetrode sputtering apparatus and a sample is prepared on a glass substrate or crystal substrate at a deposition rate of about 1 ⁇ m/hr by evacuating previously the vacuum chamber to a vacuum degree of 1 ⁇ 10 -8 Torr, introducing high purity argon gas with keeping the pressure at 2-8 ⁇ 10 -4 Torr, applying a voltage to the anode with varying from 60 V to 150 V and applying a high frequency voltage of ⁇ 1-2 KV to the target.
- This deposited material has a rocksalt-type crystalline structure and an electrical resistivity of about 4 ⁇ 10 -4 ⁇ cm.
- the relative ratio of the components of the deposited metallic modified material can be controlled by controlling the composition of one body target consisting of two kinds of semiconductors or by controlling the effective areas of two kinds of targets arranged separately.
- a metallic modified material having a rocksalt structure of indium arsenide (InAs) shows a lattice constant of 5.73 A and density of 6.71 g/cm 3 at normal pressure and room temperature
- another metallic modified material having a rocksalt structure of indium antimonide (InSb) shows a lattice constant of 6.11 A and density of 6.92 g/cm 3 .
- a ternary system metallic modified material of indium, antimony and arsenic with a composition ratio of 0 ⁇ 1 is deposited from one body target consisting of a combination of indium antimonide and indium arsenide or from targets arranged separately.
- a metallic modified material having a rocksalt-type crystalline structure of intermetallic compound consisting of at least three components is deposited from two kinds of zincblende-type semiconductor targets consisting of at least two components selected from the foregoing elements and at least one reactive gaseous composition containing at least one components selected from the foregoing elements.
- a target consisting of a combination of two kinds of semiconductors as described above is fitted to a tetrode sputtering apparatus and a metallic modified material consisting of at least three components is deposited on a glass substrate plate or crystal substrate plate by evacuating previously the vacuum chamber to a vacuum degree of 1 ⁇ 10 -8 Torr, introducing thereinto a gaseous mixture of high purity argon gas and at least one reactive gaseous composition containing at least one component of semiconductor with keeping the pressure at 2-8 ⁇ 10 -4 Torr, applying a voltage to the anode with varying from 60 V to 150 V and applying a high frequency voltage of ⁇ 1-2 kV to the target, thereby inducing sputtering of the target and decomposition and ionization of the reactive gaseous composition.
- the important advantage of this method consists in that a reactive gas such as AsH 3 or PH 3 is decomposed by discharge in a tetrode sputtering apparatus, mixed with the component gases transported by sputtering from a target consisting of a combination of two kinds of semiconductors and there is thus deposited on a substrate plate a metallic modified material controlled stoichiometrically and bonded homogeneously.
- a reactive gas such as AsH 3 or PH 3
- a metallic modified material with a stoichiometric ratio but also a metallic modified material with a non-stoichiometric ratio but being controlled in deviation from the stoichiometric ratio can be deposited by controlling the partial pressure of a reactive gas containing the component.
- FIG. 8 shows an example of heterojunction device wherein a metallic modified material of InSb 2 is deposited on a substrate plate 1 of a semiconductor crystal such as Si, Ge, InSb, GaAs, GaP, etc. by tetrode sputtering, 3 being an SiO 2 insulating film and 4 being an electrode.
- FIG. 9 shows an example of semiconductor-superconductor heterojunction device used at a low temperature, having a multi-layer structure of a semiconductor film 1 and metallic modified film 2 of InSb obtained by controlling the anode voltage of tetrode sputtering. Futhermore, in the ternary system and quaternary (four component) system metallic modified materials according to the present invention, the lattice constant can be changed by the composition thereof, thus making easier controlling of the lattice for a heterojunction.
Abstract
The present invention is concerned with a new metallic modified material of intermetallic compound, which has the same chemical composition as an intermetallic compound semi-conductor with a zincblende-type or wurtzite-type crystalline structure and further has a rocksalt-type crystalline structure and which is stable at room temperature under atmospheric pressure to a high pressure.
Description
This is a continuation, of application Ser. No. 886,581, filed Mar. 14, 1978, now abandoned.
1. Field of the Invention
The present invention relates to a new metallic modified material having the same chemical composition as an intermetallic compound semiconductor but differing in crystalline structure and a process for the production of the same.
2. Description of the Prior Art
As an intermetallic compound semiconductor, there are known Group III-V compounds having a zincblende-type or wurtzite-type crystalline structure such as InSb, InAs, InP, GaSb, GaAs, GaP, etc., Group II-VI compounds such as ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, BeO, etc., Group I-VII compounds such as CuCl and Group IV-VI compounds having a rocksalt type crystalline structure such as PbS, PbSe, PbTe, SnTe, etc. On the other hand, it is known that amorphous semiconductors of intermetallic compounds are formed on substrates by vacuum deposition method or by sputtering method. When intermetallic compound semiconductors are exposed to a high pressure at room temperature, for example, InSb, GaSb, AlSb, etc. are transformed into a white-tin-type crystalline structure and InAs, InP, ZnSe, ZnTe, CuCl, etc. are transformed into a rocksalt type crystalline structure, thus behaving themselves like a metal. However, phase transition into the semiconductor phase takes place when the pressure is lowered to normal pressure. It is also known that the high pressure metallic phase of Group III-V compounds is obtained as a metastable phase when the pressure is lowered to normal pressure at 77° K.
The inventors have previously reported that an amorphous InSb semiconductor is transformed into a material of rocksalt-type crystalline structure under a high pressure such as of about 10 Kbar, which is further transformed into a material of white-tin-type crystalline structure under a high pressure such as about 30 Kbar and which is transformed into a mixture of zincblende-type crystalline structure and rocksalt-type crystalline structure when the pressure is lowered to normal pressure. Thus, this is unstable under high pressures.
It is an object of the present invention to provide a novel metallic modified material having the same chemical composition as an intermetallic compound semiconductor but differing in crystal structure.
It is another object of the present invention to provide a novel metallic modified material suitable for use in heterojunction devices.
It is a further object of the present invention to provide a process for the production of a metallic modified material of intermetallic compound by sputtering.
These objects can be attained by a metallic modified material of intermetallic compound, which has the same chemical composition as an intermetallic compound semiconductor with a zincblende-type or wurtzite-type crystalline structure and further has a rocksalt-type crystalline structure and which is stable at room temperature to a predetermined temperature under normal pressure to high pressure, and by a process for the production of a metallic modified material of intermetallic compound which comprises depositing from a target consisting of an intermetallic compound semiconductor with a zincblende-type or wurtzite-type crystalline structure a metallic modified material of intermetallic compound with a rocksalt crystalline structure and the same chemical composition as the target on a substrate by tetrode-type sputtering.
The accompanying drawings are to illustrate the principle and merits of the present invention in more detail.
FIG. 1 is a schematic view of tetrode-type sputtering system used in the present invention,
FIG. 2 is a graph showing the relation of the threshold value of anode voltage and the current,
FIG. 3 is X-ray diffraction patterns of rocksalt-type InSb and zincblende-type InSb for comparison,
FIG. 4 is a graph showing the results of differential thermal analysis as to the metallic modified material of InSb having a rocksalt crystalline structure according to the present invention,
FIG. 5 are photoelectron spectra of valence bands of the metallic modified material (a) consisting of rocksalt-type InSb and zincblende-type single crystal semiconductor (b),
FIG. 6 is a graph showing the thermal effect of from room temperature to 4.2° K. on the resistivity of the metallic modified material of InSb,
FIG. 7 is a graph showing the change of volume and lattice constant with pressure,
FIG. 8 is a cross sectional view of a heterojunction device consisting of a thin film and substrate and
FIG. 9 is a cross sectional view of a semiconductor-superconductor heterojunction device consisting of a multilayer of thin films and substrates.
In accordance with the present invention, there is provided a metallic modified material (metallic modifications) of intermetallic compound, which has the same composition as an intermetallic compound semiconductor with a zincblende type or wurtzite type crystalline structure and further has a rocksalt-type crystalline structure and which is stable at room temperature to a predetermined temperature under atmospheric pressure to high pressures. In the present invention, the intermetallic compound is selected from the group consisting of Group III-V compounds, Group II-VI compounds, Group I-VII compounds, Group IV-VI compound-containing mixtures with these compounds and mixtures thereof. The deposition can be carried out in the presence of at least one reactive gaseous composition comprising at least one component selected from Group II, III, IV, V and VI elements.
In one embodiment of the present invention, from a target of a zincblende-type semiconductor consisting of two components selected from Group III elements and Group V elements is deposited the metallic modified material of intermetallic compound having the same chemical composition as the target and a rocksalt-type crystalline structure on a substrate by tetrode sputtering.
In another embodiment of the present invention, from a target consisting of a combination of two kinds of semiconductors of Group III-V compounds with other Group III-V compounds, Group IV elements or Group II-VI compounds is deposited a metallic modified material of intermetallic compound consisting of at least three components, the content of the each component being 1% or more, and having a rocksalt-type crystalline structure on a substrate by tetrode sputtering.
In a further embodiment of the present invention, from a target consisting of a combination of two kinds of semiconductors of Group III-V compounds with other Group III-V compounds, Group IV elements or Group II-VI compounds and at least one reactive gaseous composition comprising at least one component selected from the above described elements is deposited a metallic modified material of intermetallic compound consisting of at least the three components, the content of the each component being 1% or more, and having a rocksalt-type crystalline structure on a substrate by discharge using a tetrode sputtering apparatus.
These metallic modified material of intermetallic compounds can be deposited on a glass substrate, single crystal substrate or polycrystalline substrate as a bulky sample by controlling the anode voltage of a tetrode sputtering apparatus to a threshold value or more. According to the present invention, it is further found that the crystalline structure of such a metallic modified material is controlled by the anode voltage of tetrode sputtering but is independent on the variety or state of a substrate and on the deposition rate on a substrate.
The present invention will now be illustrated in detail by the accompanying drawings.
FIG. 1 shows a schematic view of tetrode sputtering apparatus suitable for the purpose of depositing a metallic modified material of intermetallic compound having a rocksalt-type crystalline structure. In this system, four electrodes, i.e., cathode 1, anode 2, target 3 and auxiliary anode (stabilizer) 4 are arranged and substrate 5 is fitted to the surface of substrate holder 6 in parallel to target 3 to be apart therefrom by about 20 cm, the target having shield plate 7. Vacuum chamber 8 is evacuated from exhaust port 9 to 1×10-8 Torr and high purity argon gas is fed from inlet 10 while keeping the evacuation to keep the pressure at about 2-8×10-4 Torr. Direct current is passed through cathode 1 to emit thermoelectrons and a constant voltage of 300 V is applied to auxiliary anode 4 to bring the thermoelectrons into collision with the argon atoms and to induce ionization of the argon atoms, thus generating a plasma P. The voltage of the argon plasma is controlled by applying a certain voltage to anode 2. 11 is an inlet for a reactive gas, 12 is a radio frequency power supply, and 13, 14 and 15 are respectively direct current power supplies. When a radio frequency voltage with a constant frequency of 13.56 MHz and voltage of about ±1-2 kV is applied to the target, the surface of the target is kept negative to the plasma every half cycle and intermetallic compound semiconductor atoms are thus sputtered, thus being deposited a metallic modified material of intermetallic compound having a rocksalt type crystalline structure on the substrate. The metallic modified material of intermetallic compound according to the present invention is deposited on the substrate by applying generally to anode 2 a voltage of more than the threshold value of about 60 V, preferably, 90 to 150 V to control the voltage of argon plasma P, while a crystal of intermetallic compound or amorphous semiconductor is deposited on the substrate by applying generally a voltage of less than the threshold value of about 60 V to anode 2. The crystalline structure of such a deposited material depends on the voltage applied to anode 2. However, control of the pressure of pure argon gas introduced into vacuum chamber 8 (2-8×10-4 Torr) and the high frequency voltage applied to target 3 (±1-2 kV) does not affect the crystalline structure of a deposited material, but affects the deposition rate.
The following examples are given in order to illustrate the present invention in greater detail without limiting the same.
Firstly, a metallic modified material with a rocksalt-type crystalline structure is deposited from a semiconductor target of indium antimonide (InSb) with a zincblende-type crystalline structure.
A semiconductor target of indium antimonide is fitted to a tetrode sputtering apparatus and a sample is prepared on a glass substrate or crystal substrate at a deposition rate of about 1 μm/hr by evacuating previously the vacuum chamber to a vacuum degree of 1×10-8 Torr, introducing high purity argon gas with keeping the pressure at 2-8×10-4 Torr, applying a voltage to the anode with varying from 20 V to 150 V and applying a high frequency voltage of ±1-2 kV to the target. As a result of the X-ray diffraction test of the sample, it is found that an amorphous semiconductor is obtained at a voltage applied to the anode of about 60 V or less, while a metallic modified material having a rocksalt-type structure is obtained at about 60 V or more.
FIG. 2 is a graph showing the relation of the threshold value of anode voltage with the current, in which the right side of the threshold value shows the rocksalt-type zone and the left side shows the amorphous zone.
FIG. 3 shows X-ray diffraction patterns of the metallic modified material of indium antimonide having a rocksalt-type crystalline structure, deposited on a glass substrate by the above described method (upper graph) and the known polycrystalline semiconductor of indium antimonide having a zincblende-type crystalline structure (lower graph). The each peak is marked with the plane index. When using a clean glass substrate polished to give an optical surface, the plane (1 0 0) of the rocksalt-type polycrystal is oriented in parallel to the surface of the substrate and when the substrate is heated at 200° C., for example, the rocksalt-single crystal is obtained. X-ray diffraction test of the rocksalt-type modified material of indium antimonide teaches that it has a lattice constant of 6.11 A and a density of 6.92 g/cm3.
FIG. 4 is a graph showing the results of differential thermal analysis of the metallic modified material of indium antimonide having a rocksalt-type crystalline structure according to the present invention. This new material is exothermically transformed into a material having a zincblende-type crystalline structure at 215° C. by heating under normal pressure at a heating rate of 10° C./min but remains metastable even by heating at 200° C. for a long time. Chemical analysis of this metallic modified material by X-ray microanalyzer shows that it is very pure and consists of antimony atom and indium atom in a composition ratio of 1.00±0.01, while chemical analysis of the same material by X-ray photoemission spectra show that it has a very high purity as well as a metallic feature with a large electron density of states at the Fermi level.
FIG. 5 shows the difference of the photoelectron spectra of valence bands as to (a) the rocksalt-type metallic modified material of indium antimonide and (b) the zincblende-type single crystal semiconductor.
FIG. 6 shows the temperature effect of from room temperature to 4.2° K. on the resistivity of the metallic modified material of indium antimonide. The electrical resistivity ρ of this new material, being substantially independent upon temperatures, is about 3×10-4 /Ω.cm. The Hall coefficient RH is about 3×10-3 cm3 /C and the polarity of the Hall voltage is negative. Assuming that electric current consists of electrons only, an electron density of electric current of about 2.1×1021 cm-3 is determined from the value of the Hall coefficient. This new material shows a superconductive transition at 3.4±0.2° K. and a very high crystical magnetic field such as 9 to 10 KG. This new material can be used as a high accuracy resistor utilizing the phenomenon that the electric resistivity is independent upon temperatures.
The rocksalt-type modified material of indium antimonide deposited by tetrode sputtering shows no phase transition under a pressure of up to about 80 Kbar at room temperature. FIG. 7 shows the change of the volume and lattice constant of this new material with pressures (V/Vo and a/ao respectively). A compressibility of 2.5×10-6 bar -1 and a bulk modulus of 400 Kbar are determined from the pressure-volume curve in the 0-20 Kbar zone. The inventors have already found that an amorphous semiconductor of indium antimonide is transformed into a material with a rocksalt-type crystalline structure under a pressure of about 10 Kbar and present as the rocksalt-type modified material even if the pressure is lowered to normal pressure and have reported this in "Philosophical Magazine," 1976, Vol. 34, No. 5, page 839-849. However, the rocksalt-type modified material transformed from an amorphous semiconductor by pressure is transformed into a material of white-tin-type crystalline structure under a pressure of about 30 Kbar, which is transformed into a mixture of a zincblende-type modified material and rocksalt-type modified material if the pressure is lowered to normal pressure, which is thus different from the rocksalt-type modified material deposited by tetrode sputtering.
The physical properties of the rocksalt-type metallic modified material of indium antimonide are summarized in Table 1 with those of the known zincblende-type single crystal semiconductor for comparison.
Table 1 ______________________________________ Comparison of Physical Properties of Rocksalt-type Metallic Modified Material and Zincblende-type Single Crystal Semiconductor Rocksalt-type Zincblende-type Physical Property Unit Metal Semiconductor ______________________________________ Density g/cm.sup.3 6.92 5.80 Lattice Constant A 6.11 6.47 Compressibility kbar 2.5 × 10.sup.-3 3.5 × 10.sup.-3Bulk Modulus kbar 400 285 Stable Temp. ° C. 215 525 Stable Pressure kbar 80 30 Superconductivity ° K. 3.4 ± 0.2 No Transition Crytical Magnetic kG 9-10 No FieldElectrical cm 4 × 10.sup.-4 1 × 10.sup.-1 Resistivity Hall Coefficient cm.sup.3 /c 3 × 10.sup.-3 1 × 10.sup.2 Electron Density of Electric cm.sup.-3 2 × 10.sup.21 1 × 10.sup.16 Current ______________________________________
Secondly, a metallic modified material having a rocksalt-type crystalline structure of intermetallic compound consisting of at least three components is deposited from a target consisting of a combination of at least two kinds of semiconductors selected from Group II, Group III, Group IV, Group V and Group VI elements.
In Table 2 are shown combination examples of two kinds of semiconductor targets used for the deposition of such metallic modified materials, in which x represents a numeral of larger than about 0.01 and x+(1-x)=1.
Table 2 ______________________________________ Metallic Modified Combination of Semiconductor Material Target ______________________________________ InSb.sub.1-x Px InSb-InP InSb.sub.1-x As.sub.x InSb-InAs In.sub.1-x Al.sub.x Sb InSb-AlSb In.sub.1-x Ga.sub.x Sb InSb-GaSb In.sub.1-x Ti.sub.x Sb InSb-TlSb (InSb).sub.1-x (GaP).sub.x InSb-GaP (InSb).sub.1-x (GaAs).sub.x InSb-GaAs (InSb).sub.1-x Si.sub.x InSb-Si (InSb).sub.1-x Ge.sub.x InSb-Ge (InSb).sub.1-x Sn.sub.x InSb-Sn (InSb).sub.1-x (ZnX).sub.x InSb-ZnS (InSb).sub.1-x (ZnSe).sub.x InSb-ZnSe (InSb).sub.1-x (ZnTe).sub.x InSb-ZnTe (InSb).sub.1-x (CdS).sub.x InSb-CdS (InSb).sub.1-x (CdSe).sub.x InSb-CdSe (InSb).sub.1-x (CdTe).sub.x InSb-CdTe ______________________________________
A target consisting of a combination of two kinds of semiconductors as described above is fitted to a tetrode sputtering apparatus and a sample is prepared on a glass substrate or crystal substrate at a deposition rate of about 1 μm/hr by evacuating previously the vacuum chamber to a vacuum degree of 1×10-8 Torr, introducing high purity argon gas with keeping the pressure at 2-8×10-4 Torr, applying a voltage to the anode with varying from 60 V to 150 V and applying a high frequency voltage of ±1-2 KV to the target. This deposited material has a rocksalt-type crystalline structure and an electrical resistivity of about 4×10-4 Ωcm. The relative ratio of the components of the deposited metallic modified material can be controlled by controlling the composition of one body target consisting of two kinds of semiconductors or by controlling the effective areas of two kinds of targets arranged separately.
For example, a metallic modified material having a rocksalt structure of indium arsenide (InAs) shows a lattice constant of 5.73 A and density of 6.71 g/cm3 at normal pressure and room temperature, while another metallic modified material having a rocksalt structure of indium antimonide (InSb) shows a lattice constant of 6.11 A and density of 6.92 g/cm3.
A ternary system metallic modified material of indium, antimony and arsenic with a composition ratio of 0≦×≦1 is deposited from one body target consisting of a combination of indium antimonide and indium arsenide or from targets arranged separately.
Thirdly, a metallic modified material having a rocksalt-type crystalline structure of intermetallic compound consisting of at least three components is deposited from two kinds of zincblende-type semiconductor targets consisting of at least two components selected from the foregoing elements and at least one reactive gaseous composition containing at least one components selected from the foregoing elements. In Table 3, there are shown examples of combinations of zincblende-type semiconductor targets and reactive gases used for the deposition of such a metallic modified material, in which x is a numeral of larger than about 0.01 and x+(1-x)=1.
Table 3 ______________________________________ Metallic Modified Combination of Semi- Material conductor Targets Reactive Gas ______________________________________ InSb.sub.1-x P.sub.x InSb-InP PH.sub.3 or P(C.sub.2 H.sub.5) InSb.sub.1-x As.sub.x InSb-InAs AsH.sub.3 or As(C.sub.2 H.sub.5).sub.3 In.sub.1-x Al.sub.x Sb InSb-AlSb AlH.sub.3 or Al(C.sub.2 H.sub.5).sub.3 In.sub.1-x Ga.sub.x Sb InSb-GaSb GaH.sub.3 or Ga(C.sub.2 H.sub.5).sub.3 In.sub.1-x Tl.sub.x Sb InSb-TlSb TlH.sub.3 or Tl(C.sub.2 H.sub.5).sub.3 (InSb).sub.1-x (GaP).sub.x InSb-GaP GaH.sub.3 and PH.sub.3 (InSb).sub.1-x (GaAs).sub.x InSb-GaAs GaH.sub.3 and AsH.sub.3 (InSb).sub.1-x Si.sub.x InSb-Si SiH.sub.4 (InSb).sub.1-x Ge.sub.x InSb-Ge GeH.sub.4 (InSb).sub.1-x Sn InSb-Sn Sn(CH.sub.3).sub.4 (InSb).sub.1-x (ZnS).sub.x InSb-ZnS H.sub.2 S (InSb).sub.1-x (ZnSe).sub.x InSb-ZnSe (C.sub.2 H.sub.5).sub.2 Se (InSb).sub.1-x (ZnTe).sub.x InSb-ZnTe (C.sub.2 H.sub.5).sub.2 Te (InSb).sub.1-x (CdS).sub.x InSb-CdS H.sub.2 S (InSb).sub.1-x (CdSe).sub.x InSb-CdSe (C.sub.2 H.sub.5).sub.2 Se (InSb).sub.1-x (CdTe).sub.x InSb-CdTe (C.sub. 2 H.sub.5).sub.2 Te (InSb).sub.1-x (PbTe).sub.x InSb-PbTe (C.sub.2 H.sub.5).sub.2 Te ______________________________________
A target consisting of a combination of two kinds of semiconductors as described above is fitted to a tetrode sputtering apparatus and a metallic modified material consisting of at least three components is deposited on a glass substrate plate or crystal substrate plate by evacuating previously the vacuum chamber to a vacuum degree of 1×10-8 Torr, introducing thereinto a gaseous mixture of high purity argon gas and at least one reactive gaseous composition containing at least one component of semiconductor with keeping the pressure at 2-8×10-4 Torr, applying a voltage to the anode with varying from 60 V to 150 V and applying a high frequency voltage of ±1-2 kV to the target, thereby inducing sputtering of the target and decomposition and ionization of the reactive gaseous composition.
The important advantage of this method consists in that a reactive gas such as AsH3 or PH3 is decomposed by discharge in a tetrode sputtering apparatus, mixed with the component gases transported by sputtering from a target consisting of a combination of two kinds of semiconductors and there is thus deposited on a substrate plate a metallic modified material controlled stoichiometrically and bonded homogeneously. In the case of sputtering a target containing a volatile component, not only a metallic modified material with a stoichiometric ratio but also a metallic modified material with a non-stoichiometric ratio but being controlled in deviation from the stoichiometric ratio can be deposited by controlling the partial pressure of a reactive gas containing the component.
The metallic modified material of the present invention is available for new heterojunction devices through deposition on substrates of semiconductor crystals. FIG. 8 shows an example of heterojunction device wherein a metallic modified material of InSb 2 is deposited on a substrate plate 1 of a semiconductor crystal such as Si, Ge, InSb, GaAs, GaP, etc. by tetrode sputtering, 3 being an SiO2 insulating film and 4 being an electrode. FIG. 9 shows an example of semiconductor-superconductor heterojunction device used at a low temperature, having a multi-layer structure of a semiconductor film 1 and metallic modified film 2 of InSb obtained by controlling the anode voltage of tetrode sputtering. Futhermore, in the ternary system and quaternary (four component) system metallic modified materials according to the present invention, the lattice constant can be changed by the composition thereof, thus making easier controlling of the lattice for a heterojunction.
Claims (1)
1. A metallic modified material of InSb or alloys thereof with a rocksalt-type structure, which has the same chemical composition as an intermetallic compound semiconductor with a zincblende-type structure, which is stable at a temperature of up to 215° C. under a pressure of up to 80 Kbar, and which shows no change of structure at room temperature under the various pressures as shown in FIG. 7.
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JP52027095A JPS5811370B2 (en) | 1977-03-14 | 1977-03-14 | Metallic transformation substances of intermetallic compounds and their production method |
JP52-27095 | 1977-03-14 |
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US06/104,464 Expired - Lifetime US4238232A (en) | 1977-03-14 | 1979-12-17 | Metallic modified material of intermetallic compound |
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US6921741B2 (en) | 2000-12-06 | 2005-07-26 | The Regents Of The University Of California | Substrate structure for growth of highly oriented and/or epitaxial layers thereon |
US20030003492A1 (en) * | 2001-06-13 | 2003-01-02 | Miller Benjamin L. | Colorimetric nanocrystal sensors, methods of making, and use thereof |
US20140065799A1 (en) * | 2012-09-03 | 2014-03-06 | Intermolecular, Inc. | Methods and Systems for Low Resistance Contact Formation |
Also Published As
Publication number | Publication date |
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JPS5811370B2 (en) | 1983-03-02 |
US4225409A (en) | 1980-09-30 |
JPS53112300A (en) | 1978-09-30 |
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